Possible
Calibre is transactional,
any network delays can corrupt the sync between the what the DB part has and what the (book) file IS.
Some folk get away doing this on a NAS.
Some keep the DB local and just the book folders on the NAS

Personally, I just cloned my existing drive onto a bigger HD, and put it in my PC
Many mid-tower PC's can hold a second drive inside. Some have an external eSATA port, so speed does not suffer

Get a USB to <laptop ldrive type: SATA or PATA) cable or Case. (attach the new drive to it)
Run the Clone program ( I used Clonezilla. It dealt with dual boot drives, WD and Maxtors utilities barfed all over the clone[totally ignored GRUB and the Linux parts] )
Swap the drives (small, '0' phillips was needed, moved carrier to new drive. Booted. Windows ran Scandisk because the last recorded did not agree with the current geometry.